TWI281875B - NOx reduction composition for use in FCC processes - Google Patents

NOx reduction composition for use in FCC processes Download PDF

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TWI281875B
TWI281875B TW091133060A TW91133060A TWI281875B TW I281875 B TWI281875 B TW I281875B TW 091133060 A TW091133060 A TW 091133060A TW 91133060 A TW91133060 A TW 91133060A TW I281875 B TWI281875 B TW I281875B
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oxide
composition
cerium oxide
catalyst
weight
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TW091133060A
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TW200300364A (en
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C P Kelkar
David M Stockwell
Samuel Tauster
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Engelhard Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12—Treating with free oxygen-containing gas
    • B01J38/30—Treating with free oxygen-containing gas in gaseous suspension, e.g. fluidised bed
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
    • Y10S502/515—Specific contaminant removal

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

A composition for controlling NOx emissions during FCC processes comprises (i) an acidic oxide support, (ii) cerium oxide, (iii) a lanthanide oxide other than ceria such as praseodymium oxide, and (iv), optionally, an oxide of a metal from groups Ib and IIb such as copper, silver and zinc.

Description

1281875 經濟部智慧財產局員工消費合作社印製 A7 _ _ B7五、發明説明（1 ) 發明背景 一個主要的工業問題涉及開發有效的降低空氣污染物 濃度的方法，污染物如由處理及燃燒含硫、碳及氮的燃料 所生成廢氣中的一氧化碳、硫氧化物及氮氧化物。這些廢 氣流排放到大氣時，其中硫氧化物、一氧化碳及氮氧化物 在傳統操作中經常遇到的濃度下對環境而言是不理想的。 因含硫及氮的烴給料之催化裂解中焦碳沉積而失去活性的 裂解觸媒之再生是一種可能導致含相當高水平的一氧化 碳、硫及氮氧化物的廢氣之典型程序之例子。 重石油餾分的催化裂解是將原油轉變爲有用的產物， 如內燃機所用之燃料的主要提煉操作之一。在流化催化裂 解法中，高分子量烴液體及蒸氣會與熱的、細分、固狀觸 媒粒子相接觸，可能於流化床反應器中或延長型轉移管線 反應器中，並以流化或分散狀態保持於高溫下足夠促成合 意裂解程度的一段時間，以裂解爲低分子量的烴，這種烴 通常存在於發動機用的汽油及蒸餾燃料中。 在烴催化裂解中，一些非揮發性含碳物質或焦炭會在 觸媒粒子上沉積。焦炭包括高縮合性芳香烴，且通常含有 約4至10重量％的氫。當烴給料包含有機硫及氮化合物 時，焦炭也會包含硫及氮。由於焦炭會在裂解觸媒上累 積，因此用以裂解的觸媒所具活性，及用以產生汽油混合 料所用觸媒的選擇性都回爲之減低。透過焦炭沉積而被實 質第抑活化的觸媒要不斷地從反應區移出。這些失去活性 的觸媒轉移到一個淸除區，於該處在高溫下使用惰性氣體 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -5- 1281875 A7 B7 五、發明説明（2) 去除揮發性沉積物。然後經由在適當的再生方法中實質地 移除焦炭沉積物而將觸媒粒子再活化至基本上其原始能 力。隨後將經再生的觸媒連續地送回到反應區以重複該循 環。 觸媒再生是通過使用含氧氣的氣體，如空氣將觸媒表 面的焦炭沉積燃燒掉而完成的。焦炭沉積的燃燒可簡單地 認爲是碳的氧化作用，且其產物爲一氧化碳和二氧化碳。 當含硫及氮的給料用於催化裂解法之中時，沉積在觸 媒的上焦炭含有硫及氮。在因焦炭而失去活性的觸媒之再 生過程中，焦炭自觸媒表面燃燒後，使得硫轉化爲硫氧化 物，且氮轉化爲氮氧化物。 觸媒在流體催化裂解（FCC)單元中所經歷的條件是十分 嚴峻的。觸媒不斷的循環於反應器側的還原性氣圍與再生 器側的氧化性氣圍之間。兩區之間的溫度不同，使得觸媒 經受到熱衝擊。再生器也標稱地含有約15_25%的蒸汽。所 有這些因素導致觸媒活性的顯著下降，且需不斷地添加新 的觸媒以保持裂解活性。 經濟部智慧財產局員工消費合作社印製 有各種方法經用來降低有毒氣體的產生或在其形成後 的處理中。最通常的方法是，使用添加劑作爲FCC中觸媒 粒子的整體部分，或作爲與FCC觸媒的摻合物中的獨立粒 子。 到目前爲止獲得廣泛接受用以在FCC單元（FCCU)中降 低硫氧化物排放的添加劑是基於氧化鎂/鋁酸鎂/二氧化姉技 術。承載在粘土或礬土上的鉑最常用爲降低一氧化碳排放 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -6 - 1281875 經濟部智慧財產局員工消費合作社印製 A7 B7五、發明説明（3) 的添加劑。不幸的是，用以控制C0排放的添加劑通常會引 發自再生器發出的N〇x之大量增加（如>300%)。 各種方法經用來處理FCCU中的含氮氧化物氣體。如 US 5,037,53 8中闡述了經由添加deN〇x觸媒到FCC中以降低 氮氧化物（N〇x)自FCC的排放，其形式爲使得deN〇x觸媒在 FCC中保持爲分離狀態。 US 5，085,762述及液態催化裂解廠的再生器中煙道氣體 內有毒的氮氧化物排放之降低，其包括在裂解觸媒循環料 中摻加個別型添加劑粒子，該添加劑粒子含有塡載銅沸石 物質，該物質具有具一界定的X-射線繞射圖樣之特性結 構。 US 5,002,654述及一種裂解觸媒的再生方法，其同時使 用基於鲜的d e N 0 X觸媒使N 0 X排放最小化。 US 5，021，146述及一種裂解觸媒的再生方法，其同時使 用基於Illb族元素的deNOx觸媒使ΝΟχ排放最小化。 US 5,364,5 17及US 5,364,5 17述及經由使用尖晶石/鈣 鈦礦添加劑降低FCC煙道氣體中的N〇x含量。 US 5,750,202及US 5,591,418述及自FCC法的氣體混合 物中去除硫氧化物或氮氧化物的方法，其中係使用一種崩 解組成物，該破裂組成物實質地由集體地具下面的通式的 微晶粒所組成： M2m2+Al2-pMp3 + Tr〇7 + r.s 一讀失閱讀背i、v>i漳) 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） -7- 1281875 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（4) 其中M2 +爲二價金屬，M3 +爲三價金屬，且T爲釩、鎢 或鉬。 US 6,1 65,933述及包括下列成分的組成物（i)酸性氧化 物載體，（ii)鹼金屬及/或鹼土金屬或彼等的混合物，（iii) 具儲存氧能力的過渡金屬氧化物，及（iv)鈀；以促進C〇 在FCC法中的燃燒，同時最小化N〇x的產生。 US 6,129,834及US 6,143,1 67述及包括下列成分的組成 物：（i)酸性氧化物載體，（ii)鹼金屬及/或鹼土金屬或彼 等的混合物，（iii)具儲存氧能力的過渡金屬氧化物，及（iv) 自元素週期表中lb族及/或lib中選取之過渡金屬；以提供 FCC法中的N〇x控制性能。 添加到F C C單元中的所有添加劑需具足夠的熱液穩定 性，以耐受住FCCU中嚴格的環境，因而有需要使要在FCC 中使用的N〇x添加劑具有改良的熱液穩定性。 發明槪述 本發明提出適用於FCC法中的新穎組成物，其可提供 改良的N〇x控制性能。 於一方面中，本發明提出用以降低FCC法中N〇x排放 的組成物，該組成物包括（i) 一酸性氧化物載體，（Π)二氧 化鈽，（iii)至少一種除二氧化鈽外的鑭系元素氧化物，及 (iv)視需要選取的，至少一種選自元素週期表中lb族及/ 或lib .中之過渡金屬的氧化物。該酸性氧化物載體較佳者爲 含有氧化鋁。氧化鐯爲二氧化鈽外較佳的鑭系氧化物。銅 (請先閲讀背面之注意事項再填寫本頁〕 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -8 - 1281875 A7 B7 五、發明説明（5) 及銀爲較佳的lb族過渡金屬，且鋅爲較佳的nb族過渡金 屬。 於另一方面中，本發明涵蓋使用本發明N〇x還原組成 物的FCC法’該組成物係作爲FCC觸媒粒子的整體部分或 作爲與FCC觸媒摻合的獨立粒子。 本發明的這些及其它方面要在下文中進一步詳述。 發明之詳細說明 本發明涵蓋下述發現，亦即某些類的組成物對於減低 在FCC法中的N〇x氣體排放量十分有效。而且，意想不到 的是此類組成物具有較先前技藝組成物改進的熱液穩定 性。本發明N〇x還原組成物之特徵在於其包括（丨）酸性氧化 物載體，（ii)鈽氧化物，（iii)至少一種除二氧化鈽外的鑭 系元素氧化物，及（iv)視需要選用的，至少一種選自元素週 期表中lb族及/或lib中之過渡金屬的氧化物，及彼等的混 合物。 經濟部智慧財產局員工消費合作社印製 酸性氧化物載體對於組成物來說應具足夠的酸性，以 作爲有效的N〇x還原添加劑。酸性氧化物觸媒載體爲諳於 此技者所熟知，且包括如過渡性氧化鋁，如7及氧化 鋁，上述氧化鋁的氧化矽穩定型，包括氧化矽穩定氧化鋁 尖晶石’其係以高嶺土特徵放熱溫度煆燒高嶺土後濾去氧 化矽以產生尖晶石，或多鋁紅柱石而形成的。該載體可爲 結晶態或非晶態。較佳者，該酸性氧化物載體含有至少一 些氧化鋁。更佳者，該氧化物載體包括至少50重量％的氧 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -9- 1281875 A7 B7 五、發明説明（6) 化鋁。該氧化物載體較佳者爲選自包括下列的群組中的氧 化物：氧化鋁及氧化矽-氧化鋁。當使用非晶態氧化矽-氧化 鋁載體時，該載體所具之氧化鋁與氧化矽莫耳比例較佳者 爲約1 : 1至高達約50 : 1。商業上可購得之酸性氧化物氧 化鋁載體的例子爲商標名爲如PURALOX，CATAPAL及 VERS AL的商品。商業上可購得之酸性氧化矽-氧化鋁載體 的例子爲商標名爲如SIRAL及SIRALOX的商品。 氧化矽-氧化鋁載體可選擇性地由自表現的高嶺土微球 體中以苛性鹼瀝濾掉氧化矽而產生，如美國專利第 4,847,225及4,628,042號中所述，該專利以引用方式倂於本 文作爲本領域的教導。較佳者爲，用於以苛性鹼瀝濾過的 高嶺土在其特徵放熱溫度下煆燒以產生尖晶體及/或多鋁紅 柱石。更佳者，該以苛性鹼瀝濾過的高嶺土載體爲微球 體，由此將以苛性鹼瀝濾過的高嶺土在放熱溫度下煆燒前 用氯羥化鋁黏合。 經濟部智慧財產局員工消費合作社印製 酸性氧化物載體更佳者更具足夠的表面積，以有助於 N〇x還原法。較佳者，該氧化物載體具至少20平方米/克的 表面積，更佳者爲約50至約300平方米/克。該酸性氧化物 載體可爲粉末，該粉末較佳地用作液態催化裂解觸媒的整 體部分，當用作與液態催化裂解觸媒混合物時，較佳者爲 微球體或粒子。 N〇x還原組成物中鈽氧化物（二氧化姉）的量相對於酸性 氧化物載體的量可能顯著地變異。較佳者，N〇x還原組成物 中每100重量份的酸性氧化物載體物質中的二氧化鈽約0.5 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -10- 1281875 A7 B7 五、發明説明（7) 重量份，更佳者爲，每100重量份的酸性氧化物載體物質 中的二氧化鈽質量約1重量分至約2 5重量份。 除二氧化鈽外的鑭系元素氧化物包括至少一種具與二 氧化鈽的儲存氧能力相似之儲存氧能力的金屬氧化物。更 佳者’ g亥除一氧化鈽外的鑭系元素氧化物爲氧化鐯。存在 於N〇x還原組成物中除二氧化鈽外的鑭系元素氧化物，其 量相對酸性氧化物載體的量可能顯著地變異。較佳者，N〇x 還原組成物中每100重量份的酸性氧化物載體物的氧化物 約0.05重量份，更佳者，每1〇〇重量份的酸性氧化物載體 物質中’ g亥除一^興化鋪外續系兀素氧化物的量爲約1重量 分至約25重量份。在本發明N〇x還原組成物中該二氧化铈 對該除二氧化鈽外鑭系元素氧化物的重量比爲1 : 4至4 : 1，較佳者爲1 : 2至2 : 1。 經濟部智慧財產局員工消費合作社印製 lb族及/或lib族過渡金屬可爲選自元素週期表中該等 族金屬中的任一金屬或金屬化合物。較佳者，該過渡金屬 係選自銅、銀、鋅及彼等的混合物中。過渡金屬的含量較 佳者爲每百萬部分的該氧化物載體物質中至少約100重量 份（以金屬氧化物形式測得），更佳者爲每1 〇〇重量份該氧化 物載體物質中至少約0.1至高達約5重量份。 該N 0 >；還原組成物可包括少量的其他物質，該物質較 佳者爲不會對N〇x還原功能具明顯的負面影響。該！^0<還 原組成物可基本上包括上述的（1)至（iv)項。當本發明組成 物用作FCC法中的添加劑粒子時，該N〇x還原組成物可與 塡充料組合（如粘土、氧化矽-氧化鋁、氧化矽及/或氧化鋁 ^紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） " -11 - 1281875 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（8) 等粒子）’及/或黏合劑（如氧化矽溶膠、氧化鋁溶膠、氧化 石夕氧化纟g溶膠，等），以產生適用於FCC法之粒子，較佳者 爲煆燒步驟前噴乾者。更佳者，多孔型粒子，也稱爲微球 體’是用酸性氧化物載體制成者，其典型地係經由在與個 別組成分浸漬之前或之後，將與黏合劑/塡充料組合之粉末 狀氧化物載體物質噴乾。較佳者，任一所用之添加黏合劑 或塡充料不會明顯對N〇x還原成分的表現具負面影響。 當N〇x還原組成物用作添加劑粒子時（與整合至Fcc觸 媒粒子自身相對者），N〇x還原成分在添加劑粒子中的量較 fzb者爲至少50重量％’更佳者爲至少75重量％。最佳者， 該添加劑粒子全部由N〇x還原成分組成。添加粒子較佳者 其大小適用於在FCC法中與觸媒儲料一起循環。該添加粒 子較佳者爲具平均粒子大小約20-200微米。添加粒子較佳 者爲具硏磨特性使得其可耐住FCCU的嚴格環境。 如上所述，本發明ΝΟχ還原組成物可加至FCC觸媒粒 子本身之中。在這種情況下，任一習用的FCC觸媒粒子成 分可用來與本發明N〇x還原組成物相組合。若整合至FCC 觸媒粒子中時，本發明N〇x還原組成物較佳者爲占FCC觸 媒粒子至少0.02重量％，更佳者爲約0.1至1〇重量％。 雖然本發明不限於任一特定的製造方法，不過本發明 N〇x還原組成物較佳者爲依下列程序製成： (a)將酸性氧化物載體粒子與氧化鈽源，至少一種除二 氧化鈽外的鑭系元素氧化物源，和視需要選用的至少一種 Ib/IIb族元素源供浸漬。 (請先閱讀背面之注意事項再填寫本頁) -裝· 、tr -線 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -12- 經濟部智慧財產局員工消費合作社印製 1281875 A7 _B7 ____五、發明説明（9) (b)煆燒U)步驟中的浸漬載體。 氧化物源較佳者爲金屬氧化物自身或個別金屬鹽的漿 液、溶膠及/或溶液，彼等在煆燒時分解爲氧化物，或氧化 物與鹽的組合。如果需要，可在煆燒步驟中，在每次的添 加之間分別添加入個別組成分於載體粒子。煆燒步驟較佳 者爲在約450至750°C。 N〇x還原組成物可用單獨的添加粒子，或作爲FCC觸 媒粒子的整體部分使用。如果作爲添加物，則該N〇x還原 組成物自身可形成爲適用於FCC法中的粒子。或者，N〇x 還原成分可與黏合劑、塡充料等通過任一習用的技術組 合。參閱如美國專利第5，194,413號中所述之方法，該專利 內容以引用方式倂於本文。 當本發明Ν〇χ還原成分係經整合至FCC觸媒粒子中 時，較佳者，首先形成該成分，然後與構成FCC觸媒粒子 的其它成分相組合。直接往FCC觸媒粒子中整合入Ν〇χ還 原組成物之步驟可用任一已知技術完成。適用於本目的之 技術例子揭示於美國專利第3,957,689、4,499，197、 4,542，188及4,45 8,623號中，該等專利得揭示內容以引用方 式倂於本文。 本發明組成物可用於任一習用的FCC法。典型的FCC 法進行反應的溫度爲450至650°C，觸媒再生溫度爲600至 8 50°C。本發明組成物可用於任一典型的烴給料之FCC加工 中。較佳者，本發明組成物用於包括烴給料的FCC程序 中，該給料含有超過平均量的氮，特別是殘餘的給料或具 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) .裝‘1281875 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed A7 _ _ B7 V. INSTRUCTIONS (1) BACKGROUND OF THE INVENTION A major industrial problem involves the development of effective methods for reducing the concentration of air pollutants, such as by treating and burning sulfur. Carbon monoxide, sulfur oxides and nitrogen oxides in the exhaust gas generated by carbon and nitrogen fuels. When these waste streams are released into the atmosphere, sulfur oxides, carbon monoxide and nitrogen oxides are undesirable for the environment at concentrations often encountered in conventional operations. Regeneration of cracking catalysts due to coke deposits in catalytic cracking of sulfur and nitrogen-containing hydrocarbon feedstocks is an example of a typical procedure that may result in exhaust gases containing relatively high levels of carbon monoxide, sulfur and nitrogen oxides. Catalytic cracking of heavy petroleum fractions is one of the major refining operations for converting crude oil into useful products, such as fuels for internal combustion engines. In fluid catalytic cracking, high molecular weight hydrocarbon liquids and vapors are contacted with hot, finely divided, solid catalyst particles, possibly in fluidized bed reactors or in extended transfer line reactors, and fluidized. Or the dispersed state is maintained at a high temperature for a period of time sufficient to promote a desired degree of cracking to crack into low molecular weight hydrocarbons which are typically present in gasoline and distillate fuels for engines. In hydrocarbon catalytic cracking, some non-volatile carbonaceous material or coke deposits on the catalyst particles. Coke includes highly condensable aromatic hydrocarbons and typically contains from about 4 to 10% by weight hydrogen. When the hydrocarbon feedstock contains organic sulfur and nitrogen compounds, the coke also contains sulfur and nitrogen. Since coke accumulates on the cracking catalyst, the activity of the catalyst used for cracking and the selectivity of the catalyst used to produce the gasoline mixture are reduced. Catalysts that are activated by solids through coke deposition are constantly removed from the reaction zone. These inactive catalysts are transferred to a removal zone where inert gas is used at high temperatures. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) -5-1281875 A7 B7 V. Description of the invention (2) Remove volatile deposits. The catalyst particles are then reactivated to substantially their original capacity by substantially removing the coke deposits in a suitable regeneration process. The regenerated catalyst is then continuously sent back to the reaction zone to repeat the cycle. Catalyst regeneration is accomplished by burning off the coke deposits on the catalyst surface using an oxygen-containing gas such as air. The combustion of coke deposits can be simply considered to be the oxidation of carbon and the products are carbon monoxide and carbon dioxide. When a sulfur and nitrogen containing feedstock is used in the catalytic cracking process, the upper coke deposited on the catalyst contains sulfur and nitrogen. During the regeneration of the catalyst that is deactivated by coke, the coke is burned from the surface of the catalyst to convert sulfur into sulfur oxides and nitrogen to nitrogen oxides. The conditions experienced by the catalyst in a fluid catalytic cracking (FCC) unit are severe. The catalyst is continuously circulated between the reducing gas wall on the reactor side and the oxidizing gas wall on the regenerator side. The temperature between the two zones is different, so that the catalyst is subjected to thermal shock. The regenerator also nominally contains about 15-25% steam. All of these factors result in a significant decrease in catalyst activity and the need to continually add new catalysts to maintain lytic activity. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumer Cooperatives. There are various methods used to reduce the production of toxic gases or in the treatment after they are formed. The most common method is to use an additive as an integral part of the catalyst particles in the FCC or as a separate particle in the blend with the FCC catalyst. The additives widely accepted to date to reduce sulfur oxide emissions in the FCC unit (FCCU) are based on magnesium oxide/magnesium aluminate/ceria technology. Platinum supported on clay or bauxite is most commonly used to reduce carbon monoxide emissions. This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) -6 - 1281875 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 B7 V. Description of the invention (3) Additives. Unfortunately, the additives used to control C0 emissions typically cause a large increase in N〇x (e.g., > 300%) from the regenerator. Various methods are used to treat nitrogen oxide gases in the FCCU. The release of nitrogen oxides (N〇x) from the FCC is reduced by the addition of deN〇x catalyst to the FCC as described in US 5,037,53 8 in the form of a deN〇x catalyst maintained in a separate state in the FCC. . US 5,085,762 describes a reduction in toxic nitrogen oxide emissions from flue gases in a regenerator of a liquid catalytic cracking plant, which comprises the incorporation of individual additive particles in the cracking catalyst recycle, the additive particles containing copper Zeolite material having a characteristic structure with a defined X-ray diffraction pattern. No. 5,002,654 describes a process for the regeneration of a cracking catalyst which simultaneously minimizes N0X emissions using a fresh d e N 0 X catalyst. No. 5,021,146 describes a method of regenerating a cracking catalyst which simultaneously uses a deNOx catalyst based on the Illb element to minimize radon emissions. US 5,364,5 17 and US 5,364,5 17 describe the reduction of N〇x content in FCC flue gases via the use of spinel/perovskite additives. US 5, 750, 202 and US Pat. No. 5,591, 418, the disclosure of which is incorporated herein by reference to the entire disclosure of the entire disclosure of the disclosure of the disclosure of the entire disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the disclosure of The composition of the grains: M2m2+Al2-pMp3 + Tr〇7 + rs I read the reading back i, v gt; i 漳) This paper scale applies to the Chinese National Standard (CNS) Α 4 specifications (210X 297 mm) -7- 1281875 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (4) where M2 + is a divalent metal, M3 + is a trivalent metal, and T is vanadium, tungsten or molybdenum. US 6,1,65,933 describes compositions comprising (i) an acidic oxide support, (ii) an alkali metal and/or alkaline earth metal or a mixture thereof, (iii) a transition metal oxide having oxygen storage capacity, And (iv) palladium; to promote the combustion of C〇 in the FCC process while minimizing the production of N〇x. US 6,129,834 and US 6,143,1 67 describe compositions comprising: (i) an acidic oxide support, (ii) an alkali metal and/or alkaline earth metal or a mixture thereof, (iii) a transition with oxygen storage capacity a metal oxide, and (iv) a transition metal selected from the group lb and/or lib of the periodic table; to provide N〇x control performance in the FCC process. All additives added to the F C C unit are required to have sufficient hydrothermal stability to withstand the rigorous environment of the FCCU, and there is a need for improved hydrothermal stability of the N〇x additive to be used in the FCC. SUMMARY OF THE INVENTION The present invention proposes novel compositions suitable for use in the FCC process which provide improved N〇x control performance. In one aspect, the invention provides a composition for reducing N〇x emissions in an FCC process, the composition comprising (i) an acidic oxide support, (ruthenium) ruthenium dioxide, (iii) at least one type of oxidizing removal An additional lanthanide oxide, and (iv) optionally selected at least one oxide selected from the group consisting of transition metals in the lb group and/or lib. The acidic oxide support preferably contains alumina. Cerium oxide is a preferred lanthanide oxide other than cerium oxide. Copper (please read the precautions on the back and fill out this page) This paper size applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) -8 - 1281875 A7 B7 V. Invention description (5) and silver is better a lb group transition metal, and zinc is a preferred nb group transition metal. In another aspect, the invention encompasses the FCC process using the N〇x reduction composition of the invention 'this composition as a whole of FCC catalyst particles In part or as separate particles blended with the FCC catalyst. These and other aspects of the invention are further detailed below. DETAILED DESCRIPTION OF THE INVENTION The present invention encompasses the discovery that certain types of compositions are useful for reducing the FCC. The N〇x gas emissions in the process are very effective. Moreover, it is unexpected that such compositions have improved hydrothermal stability compared to prior art compositions. The N〇x reduced composition of the present invention is characterized in that it includes (丨An acidic oxide carrier, (ii) a cerium oxide, (iii) at least one lanthanide oxide other than cerium oxide, and (iv) optionally selected, at least one selected from the group consisting of lbs of the periodic table and /or l The oxides of transition metals in ib, and their mixtures. The printed acid oxide carrier printed by the Ministry of Economic Intelligence's Intellectual Property Bureau employee consumption cooperatives should be sufficiently acidic for the composition to be an effective N〇x reduction additive. The acidic oxide catalyst support is well known to those skilled in the art and includes, for example, transitional aluminas such as 7 and alumina, the yttria-stabilized type of the above-mentioned alumina, including yttria-stabilized alumina spinel The kaolin is characterized by an exothermic temperature of kaolin, and the cerium oxide is filtered to produce spinel, or mullite. The carrier may be crystalline or amorphous. Preferably, the acidic oxide carrier contains at least Some alumina. More preferably, the oxide carrier comprises at least 50% by weight of oxygen. The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -9- 1281875 A7 B7 5. Invention Description (6) The oxide support is preferably an oxide selected from the group consisting of alumina and yttria-alumina. When an amorphous yttria-alumina support is used, the support Preferably, the alumina to cerium oxide molar ratio is from about 1:1 to up to about 50: 1. Commercially available examples of acidic oxide alumina supports are commercially available under the trade names PURALOX, CATAPAL and VERS. Commercially available commercially available cerium oxide-alumina supports are commercially available under the trade names SIRAL and SIRALOX. The cerium oxide-alumina support can be selectively causticized from self-expressing kaolin microspheres. The leaching of the cerium oxide by the alkali is produced as described in U.S. Patent Nos. 4,847,225 and 4,628,04, the disclosure of each of Its characteristic is calcined at an exothermic temperature to produce sharp crystals and/or mullite. More preferably, the caustic leached kaolin carrier is a microsphere, whereby the caustic leached kaolin is bonded with aluminum chlorohydrate prior to calcination at an exothermic temperature. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumer Cooperatives. The better the acidic oxide carrier, the more surface area is available to help the N〇x reduction method. Preferably, the oxide support has a surface area of at least 20 square meters per gram, more preferably from about 50 to about 300 square meters per gram. The acidic oxide support can be a powder which is preferably used as an integral part of a liquid catalytic cracking catalyst. When used as a mixture with a liquid catalytic cracking catalyst, it is preferably a microsphere or particle. The amount of cerium oxide (cerium oxide) in the N〇x reducing composition may vary significantly with respect to the amount of the acidic oxide carrier. Preferably, the N?x reduction composition contains about 0.5 of cerium oxide per 100 parts by weight of the acidic oxide carrier material. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -10- 1281875 A7 B7 V. Description of the Invention (7) The parts by weight, more preferably, are from about 1 part by weight to about 25 parts by weight per 100 parts by weight of the cerium oxide in the acidic oxide carrier material. The lanthanide oxide other than cerium oxide includes at least one metal oxide having a storage oxygen capacity similar to that of cerium oxide. More preferably, the lanthanide oxide other than cerium oxide is cerium oxide. The lanthanide oxides other than cerium oxide present in the N〇x reduction composition may vary significantly in amount relative to the amount of the acidic oxide carrier. Preferably, the N?x reduction composition comprises about 0.05 parts by weight per 100 parts by weight of the oxide of the acidic oxide support, and more preferably, each part by weight of the acidic oxide carrier material is removed. The amount of the external halogenated halogen oxide is from about 1 part by weight to about 25 parts by weight. The weight ratio of the cerium oxide to the lanthanide oxide other than cerium oxide in the N〇x reduction composition of the present invention is from 1:4 to 4:1, preferably from 1:2 to 2:1. The lb and/or lib transition metals printed by the Intellectual Property Office of the Ministry of Economic Affairs may be any metal or metal compound selected from the group of metals in the periodic table. Preferably, the transition metal is selected from the group consisting of copper, silver, zinc, and mixtures thereof. The transition metal content is preferably at least about 100 parts by weight (as measured as a metal oxide) per million parts of the oxide support material, more preferably in the oxide support material per 1 part by weight At least about 0.1 up to about 5 parts by weight. The N 0 > reduction composition may include minor amounts of other materials which, preferably, do not have a significant negative impact on the N〇x reduction function. That! The ^0<reduction composition may substantially include the above items (1) to (iv). When the composition of the present invention is used as an additive particle in the FCC process, the N〇x reduction composition can be combined with a ruthenium charge (such as clay, yttria-alumina, yttria and/or alumina). National Standard (CNS) A4 Specification (210X297 mm) " -11 - 1281875 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 5, Invention Description (8) Particles' and/or Adhesives (such as Antimony Oxide) Sol, alumina sol, oxidized cerium oxide sol sol, etc.) to produce particles suitable for use in the FCC process, preferably those sprayed before the simmering step. More preferably, the porous particles, also referred to as microspheres, are made from an acidic oxide support, typically via a powder that is combined with the binder/tank charge before or after impregnation with the individual components. The oxide carrier material is spray dried. Preferably, any of the added binders or ruthenium fillers used do not significantly adversely affect the performance of the N?x reducing component. When the N〇x reduction composition is used as an additive particle (as opposed to being integrated into the Fcc catalyst particle itself), the amount of the N〇x reduction component in the additive particle is at least 50% by weight compared to the fzb', and more preferably at least 75 wt%. Most preferably, the additive particles are all composed of N〇x reducing components. Preferably, the addition of particles is sized to circulate with the catalyst stock in the FCC process. Preferably, the added particles have an average particle size of from about 20 to about 200 microns. Adding particles is preferably a rigorous environment with honing properties that allows them to withstand FCCU. As described above, the ruthenium reduction composition of the present invention can be added to the FCC catalyst particles themselves. In this case, any conventional FCC catalyst particle component can be used in combination with the N〇x reducing composition of the present invention. When incorporated into FCC catalyst particles, the N?x reduction composition of the present invention preferably comprises at least 0.02% by weight of the FCC catalyst particles, more preferably from about 0.1 to 1% by weight. Although the invention is not limited to any particular method of manufacture, the N〇x reduction composition of the invention is preferably prepared according to the following procedure: (a) at least one of the acidic oxide carrier particles and the cerium oxide source. An external source of lanthanide oxide, and optionally at least one source of Ib/IIb element for impregnation. (Please read the note on the back and fill out this page) -Installation, tr-line paper size applicable to China National Standard (CNS) A4 specification (210X297 mm) -12- Printed by the Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative 1281875 A7 _B7 ____ V. INSTRUCTIONS (9) (b) The impregnated carrier in the U) step. The oxide source is preferably a slurry, a sol and/or a solution of the metal oxide itself or an individual metal salt which decomposes into an oxide or a combination of an oxide and a salt upon calcination. If desired, individual components can be added to the carrier particles between each addition during the calcination step. The calcining step is preferably at about 450 to 750 °C. The N〇x reduction composition can be used as a separate additive particle or as an integral part of the FCC catalyst particle. If used as an additive, the N?x reduction composition itself can be formed into particles suitable for use in the FCC process. Alternatively, the N?x reducing component can be combined with any of the conventional techniques, such as binders, enamels, and the like. See, for example, the method described in U.S. Patent No. 5,194,413, the disclosure of which is incorporated herein by reference. When the quinone reducing component of the present invention is incorporated into the FCC catalyst particles, it is preferred to first form the component and then combine with other components constituting the FCC catalyst particles. The step of integrating the ruthenium reduction composition directly into the FCC catalyst particles can be accomplished by any known technique. Examples of the techniques that are suitable for this purpose are disclosed in U.S. Patent Nos. 3,957,689, 4, 499, 197, 4, 542, 188, and 4, 458, 623, the disclosures of each of which are incorporated herein by reference. The composition of the present invention can be used in any conventional FCC process. The typical FCC method is carried out at a temperature of 450 to 650 ° C and a catalyst regeneration temperature of 600 to 850 ° C. The compositions of the present invention can be used in FCC processing of any typical hydrocarbon feedstock. Preferably, the composition of the present invention is used in an FCC process comprising a hydrocarbon feedstock containing more than an average amount of nitrogen, in particular a residual feedstock or a paper scale applicable to the Chinese National Standard (CNS) Α4 specification (210X297 mm). (Please read the notes on the back and fill out this page).

、1T -線 -13- 1281875 A7, 1T - line -13- 1281875 A7

五、發明説明（1〇 (請先閲讀背面之注意事項再填寫本頁) 至少0.1重量％含氮量的給料。所用本發明Ν〇χ還原成分的 重可變化，取決於特定的FCC法。較佳者，該Ν〇χ還原成 分的用量（在循環儲料中），以Fcc裂解觸媒在循環觸媒儲 料中的重量爲基準，爲約〇.丨至15重量％。在FCC法觸媒 再生步驟中本發明組成物的存在可大幅降低再生過程中Ν〇χ 的排放水平，同時具改進的熱液穩定性。 實施例1 2%Pr6〇ii/10%Ce〇2/2%Cu〇/氧化鋁 將氧化鋁載體粒子與鈽及鐯的硝酸鹽之溶液以初始濕 度一同浸漬，乾燥，並在1 200T下煆燒2個小時，以達到 10%CeCh及2重量％ Pr6〇u的水平。在微球體上，浸漬硝酸 銅，乾燥，並在1 200°F下煆燒2個小時，以達到2重量％的 C u〇水平。 實施例2 經濟部智慧財產局w工消費合作社印製 3%La2〇3/10% Ce〇2/3%Nch〇3/2% Cu〇 /氧化鋁 將氧化鋁載體粒子與鑭、鈽及銨的硝酸鹽溶液以初始 濕度一同浸漬，乾燥，並在1200°F下煆燒2個小時，以達 到10% 〇6〇2及2重量％ NchCh的水平。在微球體上，浸漬 硝酸銅，乾燥，並在1 200°F下煆燒2個小時，以達到2重 量％的CuO水平。 實施例3 本紙張尺度適用中國國家標準（CNS ) A4規格（210><297公釐） -14- 1281875 A7 經濟部智慧財產局員工消費合作社印製 一__B7五、發明説明（1》 2% Ρι·6〇ι〗/10% Ce〇2/2%Cu〇/氧化鋁 將氧化鋁載體粒子與鋪、鐯及銅的硝酸鹽溶液以初始 濕度一同浸漬，乾燥，並在1200°F下煆燒2個小時，以達 到 10% Ce〇2/2%Pr6〇H/2% Cu〇水平。 實施例4 氧化鋁上 2% Ρι·6〇η/10% Ce〇2/1.5% Nd2Ch/2% Cu〇 將氧化鋁載體粒子與铈、鐯及銨的硝酸鹽溶液以初始 濕度一同浸漬，乾燥，並在1200° F下煆燒2個小時，以達 到10% Ce〇2/10重量％Ρι·6〇η及1.5% Nd2〇3水平。在微球體 上，浸漬硝酸銅，乾燥，並在1200° F下煆燒2個小時，以 達到2重量％的Cu〇水平。 比較實施例 實施例A 氧化鋁上3% Na2〇/10% Ce〇2/2% Cu〇 將氧化鋁載體粒子與硝酸鈉溶液以初始濕度一同浸 漬，乾燥，並在1200° F下煆燒2個小時，以達到3.0重量 %的Na2〇。含鈉氧化鋁粒子與鈽及銅的硝酸鹽溶液一同浸 漬，在1 200° F下煆燒2個小時，以達到10重量％的 CeCh，2% Cu〇水平。 實施例B 氧化鋁上5%Mg〇/10% Ce〇2/2%Cu〇 (請先閱讀背面之注意事項再填寫本頁) -裝·V. INSTRUCTIONS (1 〇 (Please read the note on the back and then fill out this page) At least 0.1% by weight of nitrogen-containing feedstock. The weight of the ruthenium reduction component of the present invention used may vary depending on the particular FCC process. Preferably, the amount of the rhodium reducing component (in the circulating stock) is from about 〇.丨 to 15% by weight based on the weight of the Fcc cracking catalyst in the recycled catalyst stock. The presence of the composition of the present invention in the catalyst regeneration step can greatly reduce the level of ruthenium emissions during regeneration, while having improved hydrothermal stability. Example 1 2% Pr6〇ii/10%Ce〇2/2% Cu〇/alumina The solution of the alumina carrier particles and the nitrates of cerium and lanthanum is impregnated together with the initial humidity, dried, and calcined at 1 200T for 2 hours to reach 10% CeCh and 2% by weight of Pr6〇u. Level: On the microspheres, impregnated with copper nitrate, dried, and simmered at 1 200 °F for 2 hours to reach a C u 〇 level of 2% by weight. Example 2 Ministry of Economic Affairs Intellectual Property Bureau w consumer consortium Printing 3% La2〇3/10% Ce〇2/3% Nch〇3/2% Cu〇/Alumina to alumina carrier particles The nitrate solution with cerium, lanthanum and ammonium was impregnated together with the initial humidity, dried and calcined at 1200 °F for 2 hours to reach a level of 10% 〇6〇2 and 2% by weight of NchCh. On the microspheres Immersed copper nitrate, dried, and calcined at 1 200 °F for 2 hours to reach a CuO level of 2% by weight. Example 3 This paper scale applies to the Chinese National Standard (CNS) A4 specification (210><297 -14- 1281875 A7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed one __B7 five, invention description (1) 2% Ρι·6〇ι〗/10% Ce〇2/2%Cu〇/alumina The alumina carrier particles are impregnated with the nitrate solution of the paving, bismuth and copper together with the initial humidity, dried, and calcined at 1200 °F for 2 hours to reach 10% Ce〇2/2%Pr6〇H/2 % Cu〇 level. Example 4 2% on alumina. Ρι·6〇η/10% Ce〇2/1.5% Nd2Ch/2% Cu〇 Initialization of alumina carrier particles with cerium, lanthanum and ammonium nitrate solutions The humidity was immersed together, dried, and calcined at 1200 ° F for 2 hours to reach 10% Ce〇2/10 wt% Ρι·6〇η and 1.5% Nd2〇3 levels. The copper nitrate was immersed, dried, and calcined at 1200 ° F for 2 hours to reach a Cu bismuth level of 2% by weight. Comparative Example Example A 3% Na2〇/10% Ce〇2/2 on alumina % Cu〇 The alumina carrier particles were impregnated with the sodium nitrate solution together with the initial humidity, dried, and calcined at 1200 °F for 2 hours to reach 3.0% by weight of Na2〇. The sodium-containing alumina particles were immersed together with a solution of cerium and copper nitrate and calcined at 1 200 °F for 2 hours to achieve a CeCh, 2% Cu 〇 level of 10% by weight. Example B 5% Mg 〇 / 10% Ce 〇 2 / 2% Cu 氧化铝 on alumina (Please read the back of the note first and then fill out this page) - Packing

、1T 線 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） -15- 1281875 經濟部智慧財產局W工消費合作社印製 A7 ______ B7_五、發明説明（q 將氧化鋁載體粒子與硝酸鎂溶液以初始濕度一同浸 漬，乾燥，並在1200° F下煆燒2個小時，以達到5.0%的 MgO水平。含鎂氧化鋁粒子與鈽及銅的硝酸鹽溶液一同浸 漬’在1200° F下煆燒2個小時，以達到10重量％的 Ce〇2，2重量％ Cu〇水平。 實施例C 氧化鋁上10% Ce〇2 將氧化鋁載體粒子與硝酸鈽溶液以初始濕度一同浸 漬，乾燥，並在1200° F下煆燒2個小時，以達到10%的 CeCh水平。 實施例ϋ 氧化鋁上10% Pr6〇n 將興化錦載體fez子與硝酸譜溶液以初始濕度一^同浸 漬，乾燥，並在1200° F下煆燒2個小時，以達到10%的 Pl.6〇H 7jC 平。 如上所述，熱液穩定性是液態催化裂解觸媒及添加劑 的一項重要性質。本技術中已知有不同的方式來實施實驗 室中FCC觸媒及添加劑所加速的熱液去活性作用。最常用 的熱液實驗室去活性步驟爲於100%蒸汽存在中，溫度介於 1 3 00至1 500° F間，蒸汽處理觸媒或添加劑4至8個小 時。受測試的添加劑在100%蒸汽中，在1500° F下蒸汽處 理4個小時即失去活性。在1000° F的氫中還原後，於室溫 (請先閱讀背面之注意事項再填寫本頁) -裝. 訂 線 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -16- 1281875 A7 B7 五、發明説明（1? 下測量添加劑上的N〇攝取。使用實施例1 -4及A-D進行的 N〇攝取測試所獲之數據如下面表1所示。NO攝取保留量 爲蒸汽處理後保留下來的NO攝取能力百分比。 表1 N〇攝取量X 1〇5 莫耳/克 N〇攝取保留量，％ (剛經蒸氣處理） 實施例A 1.39 22 實施例B 1.13 28 實施例C 0.75 30 實施例D 0.58 32 實施例1 4.45 65 實施例2 4.9 67 實施例3 4.61 67 實施例4 3.58 64 如可看出者，實施例1至4，屬本發明範疇之內者，產生實 質的NO攝取，及相對於實施例A至D的NO攝取保留量。 特別意想不到者，測試結果中在單獨的氧化鈽及氧化鐯之 各自測試中產生很少量的NO攝取（實施例C及D)。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝 訂 線, 1T line paper size applies to China National Standard (CNS) Α 4 specifications (210Χ 297 mm) -15- 1281875 Ministry of Economic Affairs Intellectual Property Bureau W industrial consumption cooperative printed A7 ______ B7_ five, invention description (q will alumina carrier The particles are impregnated with the magnesium nitrate solution at the initial humidity, dried, and calcined at 1200 ° F for 2 hours to achieve a MgO level of 5.0%. The magnesium-containing alumina particles are impregnated with the nitrate solution of cerium and copper. The crucible was calcined at 1200 ° F for 2 hours to reach 10 wt% Ce〇2, 2 wt% Cu〇 level. Example C 10% Ce〇2 on alumina The alumina carrier particles and cerium nitrate solution were initially humidified. They were immersed together, dried, and calcined at 1200 ° F for 2 hours to reach a CeCh level of 10%. Example 10 10% Pr6〇n on alumina The initial solution was prepared with a solution of Xinghuajin carrier fez and nitric acid Immersed, dried, and simmered at 1200 ° F for 2 hours to reach 10% of Pl.6〇H 7jC. As mentioned above, hydrothermal stability is a liquid catalytic cracking catalyst and additive Important nature of the item. Different ways are known in the art. Performs thermal fluid deactivation accelerated by FCC catalysts and additives in the laboratory. The most common hydrothermal laboratory deactivation step is in the presence of 100% steam at temperatures between 1 300 and 1500 ° F, steam Treat the catalyst or additive for 4 to 8 hours. The tested additive loses activity after steaming at 1500 ° F for 4 hours in 100% steam. After reduction in 1000 ° F hydrogen, at room temperature (please Read the notes on the back and fill out this page. - Packing. The paper size applies to the Chinese National Standard (CNS) A4 size (210X 297 mm) -16- 1281875 A7 B7 V. Description of the invention (1? N〇 uptake on the additive. The data obtained by the N〇 uptake test using Examples 1-4 and AD are shown in Table 1 below. The NO uptake retention is the percentage of NO uptake remaining after steam treatment. N〇 uptake X 1〇5 mol/g N〇 uptake retention, % (just after steam treatment) Example A 1.39 22 Example B 1.13 28 Example C 0.75 30 Example D 0.58 32 Example 1 4.45 65 Example 2 4.9 67 Example 3 4.61 67 Example 4 3.58 6 4 As can be seen, Examples 1 to 4, which are within the scope of the present invention, produce substantial NO uptake and NO uptake retention relative to Examples A through D. Particularly unexpected, in the test results A small amount of NO uptake was produced in each of the separate tests of cerium oxide and cerium oxide (Examples C and D). This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the notes on the back and fill out this page).

經濟部智慧財產局員工消費合作社印製 -17-Printed by the Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative -17-

Claims (1)

A8 B8 C8 D8 1281875 A、申請專利範圍 附件2A··第9 1 1 33060號專利申請案 中文申請專利範圍替換本 民國96年2月13日修正 1 · 一種Ν Ο X去除組成物，其適用於在液態催化裂解法 的觸媒再生過程中減低NOx排放量，該組成物包括（i) 一 酸性氧化物載體，（ii)二氧化鈽，（iii)至少一種除二氧化 鈽外的鑭系元素氧化物，及（iv)視需要選用的，至少一種選 自元素週期表中lb族及/或lib中之過渡金屬的氧化物，及 彼等的混合物。 2.如申請專利範圍第1項之組成物，其中該酸性氧化物 載體係選自氧化鋁及氧化矽-氧化鋁。 3 ·如申請專利範圍第2項之組成物，其中該酸性氧化物 載體爲氧化鋁。 4·如申請專利範圍第2項之組成物，其中該酸性氧化物 載體爲氧化矽-氧化鋁。 5 ·如申請專利範圍第4項之組成物，其中該氧化矽-氧 化鋁具有約1 : 1至高達約50 : 1的氧化鋁：氧化矽摩爾比 〇 6·如申請專利範圍第4項之組成物，其中該氧化矽_氧 化鋁係經由以苛性鹼瀝濾掉煆燒高嶺土中的氧化矽而製備 成。 7·如申請專利範圍第4項之組成物，其中該氧化矽-氧 化鋁係經由以苛性鹼瀝濾掉特性放熱溫度下煆燒過的高嶺 土中的氧化矽而製備成。 本紙張尺度適用中國國家摞準（CNS ) A4規格（210X297公釐） — II-----#! (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 1281875 A8 B8 C8 D8 六、申請專利範圍 8. 如申請專利範圍第7項之組成物，其中該以苛性鹼瀝 濾過的高嶺土載體爲微球體，由此以苛性鹼瀝濾過的高嶺 土在其特性放熱溫度下煆燒之前與氯羥化鋁結合。 9. 如申請專利範圍第1項之組成物，其中該lb及lib族 過渡金屬係選自銅、銀、鋅及彼等的混合物。 10. 如申請專利範圍第1項之組成物，其中每100重量 份的該酸性氧化物載體中含有至少約0.5重量份的該二氧化 铈。 U.如申請專利範圍第1項之組成物，其中每100重量 份的該酸性氧化物載體中含有至少約0.5重量份的該除=氧 化鈽外至少一種鑭系元素氧化物。 i 2.如申請專利範圍第1項之組成物，其中每1〇〇重量 份的該酸性氧化物載體中含有至少約2至約25重量份的該 二氧化鈽。 ’ i 3.如申請專利範圍第1項之組成物，其中每1〇〇重量 份的該酸性氧化物載體中含有至少約2至約25重量份的該 除二氧化鈽外的至少一種鑭系元素氧化物。 14. 如申請專利範圍第1項之組成物，其中該除二氧化 鈽外之一種鑭系元素氧化物爲氧化鐯。 15. 如申請專利範圍第14項之組成物，其中二氧化鈽對 氧化鐯的重量比介於約1 : 4至約4 : 1。 16. 如申請專利範圍第14項之組成物，其中二氧化鈽對 氧化鐯的重量比介於約1 : 2至約2 : 1。 17. —種液態裂解觸媒組成物，其包括（a)—種適用於催 本紙張尺度適用中國國家#準（ CNS ) A4規格（210X297公釐） 77^ — II-----f, (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 1281875 A8 B8 C8 D8 六、申請專利範圍 (請先聞-tt背面之注意事項再填寫本頁) 化烴裂解的裂解性成分，及（b)—種NOx還原組成物，該組 成物包括（i) 一種酸性氧化物載體（ii)二氧化鈽（iii)至少 一種除二氧化鈽外的鑭系元素氧化物，及（iv)視需要選用的 ’至少一種選自元素週期表中lb族及/或lib中之過渡金屬 的氧化物，該NOx還原組成物爲該觸媒組成、物粒子的一整 體部分，爲觸媒成分或彼等的混合物的單獨粒子，且其係 以足夠的NOx還原量存在於裂解觸媒中。 1 8 ·如申請專利範圍第1 7項之裂解觸媒組成物，其中該 裂解觸媒包括一種成分（a)及成分（b)的混合物。 19·如申請專利範圍第17項之裂解觸媒組成物，其中該 裂解觸媒包括同時含有成分（a)及成分（b)之整合粒子。 20. 如申請專利範圍第17項之裂解觸媒組成物，其中該 N〇x還原組成物（b)包括約0.1至15重量％的該裂解觸媒組 成物。 21. 如申請專利範圍第17項之裂解觸媒組成物，其中該 除二氧化鈽外的一種鑭系元素的氧化物爲氧化鐯。 經濟部智慧財產局員工消費合作社印製 22. —種在烴給料的液態催化裂解成爲低分子量成分的 過程中降低NOx排放量之方法，該方法包括將一烴給料與 適用於催化烴裂解的裂解觸媒在高溫下接觸，由此使低分 子量的烴成分在NOx還原組成物的存在下產生，其中該 N〇x還原組成物包括（i) 一種酸性氧化物載體，（ii)每100 重量份的該酸性氧化物載體至少〇 · 5重量份的鈽氧化物， (iii)每100重量份的該酸性氧化物載體至少0.5重量份的 該除二氧化鈽外的一種鑭系元素的氧化物，及（iv)視需要選 本紙張尺度適用中國國家揉準（CNS ) A4規格（210X297公釐） 1281875 A8 B8 C8 D8 經濟部智慧財產局員工消費合作社印製 六、申請專利範圍 用的，一種自元素週期表中lb族及lib中選取之過渡金屬 的氧化物，該N〇x還原成分的含量足夠還原N〇x。 23. 如申請專利範圍第22項之方法，其中該裂解觸媒及 N〇x還原組成物包括一種單獨的裂解觸媒成分及該NOx還 原組成物成分的摻合物。 24. 如申請專利範圍第22項之方法，其中該裂解觸媒及 N〇x還原組成物包括該裂解觸媒成分及NOx還原組成物成 分的整合組合。 25·如申請專利範圍第22項之方法，其中該裂解觸媒在 與烴給料接觸時流體化。 2 6 ·如申請專利範圍第2 5項之方法，其進一步包括將用 過的觸媒自該接觸步驟中回收，且在可再生該觸媒的條件 下處理該用過的觸媒以再生該觸媒。 27·如申請專利範圍第22項之方法，其中該烴給料包括 至少0.1重量％的氮。 28·如申請專利範圍第22項之方法，其中該除二氧化铈 外的至少一種鑭系元素的氧化物爲氧化鐯。 29.如如申請專利範圍第28項之方法，其中該氧化鈽對 該氧化鐯的重量比爲約4 : 1至約1 : 4。 (請先閲囀背面之注意事項再填寫本頁) 訂 f 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -4 -A8 B8 C8 D8 1281875 A, the scope of application for patents Annex 2A · · 9 1 1 33060 Patent application Chinese patent application scope replaced by the Republic of China on February 13, 1996 1 · A Ν 去除 X removal composition, which is applicable to To reduce NOx emissions during catalyst regeneration by liquid catalytic cracking, the composition comprises (i) an acidic oxide support, (ii) cerium oxide, (iii) at least one lanthanide other than cerium oxide. An oxide, and (iv) optionally, at least one oxide selected from the group consisting of transition metals in the lb group and/or lib of the Periodic Table of the Elements, and mixtures thereof. 2. The composition of claim 1, wherein the acidic oxide support is selected from the group consisting of alumina and yttria-alumina. 3. The composition of claim 2, wherein the acidic oxide support is alumina. 4. The composition of claim 2, wherein the acidic oxide support is cerium oxide-alumina. 5. The composition of claim 4, wherein the cerium oxide-alumina has an alumina of from about 1:1 to up to about 50:1: molar ratio of cerium oxide 〇6 as described in claim 4 A composition in which the cerium oxide-alumina is prepared by leaching cerium oxide in calcined kaolin with caustic. 7. The composition of claim 4, wherein the cerium oxide-aluminum oxide is prepared by leaching cerium oxide in calcined kaolin under characteristic exothermic temperatures with caustic. This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) — II-----#! (Please read the note on the back and fill out this page.) Order the Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperative 1281875 A8 B8 C8 D8 VI. Patent Application No. 8. The composition of claim 7 wherein the caustic leached kaolin carrier is a microsphere, whereby the kaolin leached by caustic is in its characteristics. It is combined with aluminum chlorohydrate before calcination at an exothermic temperature. 9. The composition of claim 1, wherein the lb and lib transition metals are selected from the group consisting of copper, silver, zinc, and mixtures thereof. 10. The composition of claim 1, wherein the acidic oxide support contains at least about 0.5 parts by weight of the cerium oxide per 100 parts by weight of the acidic oxide support. U. The composition of claim 1, wherein the acidic oxide support contains at least about 0.5 part by weight of the lanthanide oxide and at least one lanthanide oxide per 100 parts by weight of the acidic oxide support. i. The composition of claim 1, wherein the acidic oxide support contains at least about 2 to about 25 parts by weight of the cerium oxide per 1 part by weight of the acidic oxide support. The composition of claim 1, wherein the acidic oxide carrier contains at least about 2 to about 25 parts by weight of the at least one lanthanide other than cerium oxide per 1 part by weight of the acidic oxide carrier. Elemental oxide. 14. The composition of claim 1, wherein the lanthanide oxide other than cerium oxide is cerium oxide. 15. The composition of claim 14 wherein the weight ratio of cerium oxide to cerium oxide is from about 1:4 to about 4:1. 16. The composition of claim 14, wherein the weight ratio of cerium oxide to cerium oxide is from about 1:2 to about 2:1. 17. A liquid cracking catalyst composition comprising (a) a species suitable for use in a paper scale applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 77^-II-----f, (Please read the notes on the back and fill out this page.) Order the Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumer Cooperatives, Print 1281875 A8 B8 C8 D8 VI. Apply for the patent scope (please first read the notice on the back of the tt and then fill in the page) a cracking component for hydrocarbon cracking, and (b) a NOx reducing composition comprising (i) an acidic oxide carrier (ii) cerium oxide (iii) at least one lanthanide other than cerium oxide An oxide, and (iv) optionally, at least one oxide selected from the group consisting of transition metals in the lb group and/or lib of the periodic table, the NOx reducing composition being the catalyst composition, a whole of the particle In part, separate particles of the catalyst component or a mixture thereof are present in the cracking catalyst in a sufficient amount of NOx reduction. The cracking catalyst composition of claim 17, wherein the cracking catalyst comprises a mixture of the component (a) and the component (b). 19. The cleavage catalyst composition of claim 17, wherein the cleavage catalyst comprises integrated particles comprising both component (a) and component (b). 20. The cracking catalyst composition of claim 17, wherein the N?x reducing composition (b) comprises from about 0.1 to 15% by weight of the cracking catalyst composition. 21. The cracking catalyst composition of claim 17, wherein the oxide of a lanthanide other than cerium oxide is cerium oxide. Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, Printed 22. A method for reducing NOx emissions during liquid catalytic cracking of hydrocarbon feedstocks into low molecular weight components, including a hydrocarbon feedstock and pyrolysis suitable for catalytic hydrocarbon cracking The catalyst is contacted at a high temperature whereby a low molecular weight hydrocarbon component is produced in the presence of a NOx reducing composition comprising (i) an acidic oxide support, (ii) per 100 parts by weight The acidic oxide carrier is at least 5 parts by weight of cerium oxide, (iii) at least 0.5 parts by weight of the lanthanide oxide other than the cerium oxide per 100 parts by weight of the acidic oxide carrier, And (iv) if necessary, the paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 1281875 A8 B8 C8 D8 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing six, the scope of application for patent, a kind The oxide of the transition metal selected from the lb group and the lib of the periodic table, the content of the N?x reducing component is sufficient to reduce N?x. 23. The method of claim 22, wherein the cleavage catalyst and the N?x reduction composition comprise a separate cleavage catalyst component and a blend of the NOx reductant component. 24. The method of claim 22, wherein the cleavage catalyst and the N?x reduction composition comprise an integrated combination of the cleavage catalyst component and the NOx reduction composition component. 25. The method of claim 22, wherein the cleavage catalyst is fluidized upon contact with the hydrocarbon feedstock. 2 6 - The method of claim 25, further comprising recovering the used catalyst from the contacting step and treating the used catalyst to regenerate the recyclable catalyst catalyst. The method of claim 22, wherein the hydrocarbon feedstock comprises at least 0.1% by weight of nitrogen. 28. The method of claim 22, wherein the oxide of at least one lanthanide other than cerium oxide is cerium oxide. 29. The method of claim 28, wherein the weight ratio of the cerium oxide to the cerium oxide is from about 4:1 to about 1:4. (Please read the note on the back and fill out this page.) Order f This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -4 -
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JP4443226B2 (en) 2010-03-31
US20040141898A1 (en) 2004-07-22
KR100998819B1 (en) 2010-12-06
EP1446462B1 (en) 2015-03-18
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WO2003046112A1 (en) 2003-06-05
MY134248A (en) 2007-11-30
US7045485B2 (en) 2006-05-16
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AU2002342336A1 (en) 2003-06-10
US20030098259A1 (en) 2003-05-29
US6800586B2 (en) 2004-10-05
US6852298B2 (en) 2005-02-08
CA2468152A1 (en) 2003-06-05
EP1446462A1 (en) 2004-08-18
US20040141897A1 (en) 2004-07-22
KR20040055810A (en) 2004-06-26
TW200300364A (en) 2003-06-01

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